**Sugarcane Bagasse As Potentially Low-Cost Biosorbent**

**Sugarcane Bagasse As Potentially Low-Cost Biosorbent**

DOI: 10.5772/intechopen.72153

Honória de Fátima Gorgulho, Viviane Vasques da Silva Guilharduci and Patrícia Benedini Martelli Viviane Vasques da Silva Guilharduci and Patrícia Benedini Martelli Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.72153

Honória de Fátima Gorgulho,

#### **Abstract**

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Sugarcane bagasse (SB) is one of the major residues obtained from agriculture, every year millions of tons of SB have been produced by the sugarcane agribusiness. This abundant residue has been showed potential as biosorbent in wastewater treatment. SB, *in nature* or chemically modified, has been widely reported as a promising sorbent for the removal of dyes or heavy metals from aqueous medium. The application of SB in oil sorption is rarer, especially for the treatment of used motor oil wastewater. However, in this chapter, we show that this material has good oil sorption capacity when compared to other commercial and natural sorbents. This study evaluates the effect of several coupling agents over SB in used motor oil sorption as well as the influence of surfactant in this process.

**Keywords:** engine washing wastewater, oil sorption, sugarcane bagasse, dye sorption, biomass

### **1. Introduction**

Agricultural waste by-products, such as sugarcane bagasse (SB), rice husk, coconut husk, sisal, and so on, have been extensively studied as a potential sorbent material for removing contaminants from water and wastewater [1]. These materials have many advantages such as the abundance, low cost, floatability, good flexibility and mechanical strength, and environmentally friendly properties. Besides, the potential use of several agricultural by-products as biosorbent is supported by its native adsorption capacity derived from their main constituents such as cellulose, hemicellulose, and lignin. These are polymeric structures with high content of hydroxyl and carboxyl groups, which have a strong influence in the adsorption capacity of different chemicals present in the aqueous medium.

Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons

SB, in nature or chemically modified, has been reported as a potential renewable sorbent for wastewater treatment [2, 3]. Millions of tons of SB have been generated every year by the sugarcane agribusiness, encouraging its reuse and recycling. The sugarcane industry is based mainly on the production of sugar and ethanol, which generates huge volumes of SB and sugarcane trash [4, 5]. After sugarcane is milled for juice extraction, bagasse is obtained as a residue, which corresponds to about 25% of the total weight, and is composed of approximately 40% cellulose, 24% hemicellulose, and 25% lignin. The hydroxyl groups are the most abundant and reactive sites in this biopolymer and are used to attach a variety of functional groups [6]. The higher content of cellulose in the SB biomass favors its hydrophilicity, which improves its interaction with cationic species in aqueous medium. As a result, SB has been widely used for the removal of heavy metals and dyes from wastewater [7–9].

chelating group that enhanced the metal complexation on fiber surface. Other compounds such as citric acid and phthalic anhydrides have also been used for SB modification, resulting then in an increase of adsorption capacity for these fibers [9, 13, 17, 18]. **Table 1** summarizes some studies where SB in nature or modified form is used to remove heavy metals from aque-

Sugarcane Bagasse As Potentially Low-Cost Biosorbent http://dx.doi.org/10.5772/intechopen.72153 267

With the expansion of textile sector, dyes in wastewater have become a serious environmental problem. Dyes are organic chemical compounds that appear colored due to the presence of chromophore groups such as nitrous, azo, and carbonyl [19, 20]. The release of dye waste into water bodies affects the life in aquatic environments, causing the ruining of soils and poisoning

**Metal ion SB/modification Sorption capacity (mg g−1) References** Cd2+ SB without modification 69.06 [12] Zn2+ Ethylenediaminetetraacetic dianhydride 105.26 [14]

Pb2+ Without modification 26.67 [17]

Co2+ Trimellitic anhydride 1.153 [3]

Cu2+ Tetraethylenepentamine 0.016 [18] Cu2+ Succinic anhydride 114 [15]

Co2+ Phthalic anhydride 0.561 [3]

Cr3+ Without modification 16.21 [13]

NaOH 26.41 Citric acid 17.2 NaOH/acylation with citric acid 31.28

*Pleurotus ostreatus* (U2–11) 36.31 *Lentinula edodes* (U6–1), 27.68 Basidiomycetes 39.93 *Ganoderma lucidum* (U12–6) 36.00

Cu2+ 0.979 Ni2+ 0.849

Cd2+ 196 Pb2+ 189

Cu2+ 0.935 Ni2+ 0.932

**Table 1.** SB in nature or modified as metal sorbent reported in the studies.

45.45

**1.2. Sugarcane bagasse as an adsorbent for removal of dyes**

ous environment.

#### **1.1. Sugarcane bagasse as a sorbent for heavy metals removal**

The utilization of unmodified or modified SB as an adsorbent have been described as a cheaper and effective technology for the removal of metal ions from wastewater [10, 11]. The metal ion-binding mechanism of adsorption on SB is attributed to its abundance of hydroxyl groups from cellulose, in which aqueous medium favors ion exchange or complexation with metal ions. Batch studies [12] using natural SB as a sorbent for removal of Cd(II) show the maximum adsorption at pH 6. The pH dependence of Cd(II) uptake was linked to both the surface functional groups and the metal ion species predominant in aqueous solution. The species Cd2+ and Cd(OH)+ are predominant at pH lower than 6, while the groups on surface are protonated and cannot bind to metal ions in solution. Besides, at very low pH, the surface groups are associated with the hydronium ions (H3 O+ ), negatively affecting the interaction with the metal cations. When the pH increases, the surface affinity with the metal also increases, and adsorption is improved.

The metal ion-binding capacity of SB can be intensified by the introduction of surface groups with capacity chelating as carboxylate or amine [13–15]. The introduction of carboxylic functions (−COOH) on cellulosic fiber, lignin, and hemicellulose can be performed via cyclic anhydride reaction. **Figure 1** displays an example of succinylation [16] reaction as an alternative route to attach carboxylic acid onto the cellulose.

Pereira et al. describe the chemical modification of SB by ethylenediaminetetraacetic (EDTA) dianhydride (EDTAD) in order to improve Zn2+ adsorption [14]. The EDTA molecule is a

**Figure 1.** Scheme of possible synthetic route for introduction of carboxylic groups.

chelating group that enhanced the metal complexation on fiber surface. Other compounds such as citric acid and phthalic anhydrides have also been used for SB modification, resulting then in an increase of adsorption capacity for these fibers [9, 13, 17, 18]. **Table 1** summarizes some studies where SB in nature or modified form is used to remove heavy metals from aqueous environment.

#### **1.2. Sugarcane bagasse as an adsorbent for removal of dyes**

SB, in nature or chemically modified, has been reported as a potential renewable sorbent for wastewater treatment [2, 3]. Millions of tons of SB have been generated every year by the sugarcane agribusiness, encouraging its reuse and recycling. The sugarcane industry is based mainly on the production of sugar and ethanol, which generates huge volumes of SB and sugarcane trash [4, 5]. After sugarcane is milled for juice extraction, bagasse is obtained as a residue, which corresponds to about 25% of the total weight, and is composed of approximately 40% cellulose, 24% hemicellulose, and 25% lignin. The hydroxyl groups are the most abundant and reactive sites in this biopolymer and are used to attach a variety of functional groups [6]. The higher content of cellulose in the SB biomass favors its hydrophilicity, which improves its interaction with cationic species in aqueous medium. As a result, SB has been

The utilization of unmodified or modified SB as an adsorbent have been described as a cheaper and effective technology for the removal of metal ions from wastewater [10, 11]. The metal ion-binding mechanism of adsorption on SB is attributed to its abundance of hydroxyl groups from cellulose, in which aqueous medium favors ion exchange or complexation with metal ions. Batch studies [12] using natural SB as a sorbent for removal of Cd(II) show the maximum adsorption at pH 6. The pH dependence of Cd(II) uptake was linked to both the surface functional groups and the metal ion species predominant in aqueous solution. The species Cd2+

ated and cannot bind to metal ions in solution. Besides, at very low pH, the surface groups

metal cations. When the pH increases, the surface affinity with the metal also increases, and

The metal ion-binding capacity of SB can be intensified by the introduction of surface groups with capacity chelating as carboxylate or amine [13–15]. The introduction of carboxylic functions (−COOH) on cellulosic fiber, lignin, and hemicellulose can be performed via cyclic anhydride reaction. **Figure 1** displays an example of succinylation [16] reaction as an alternative

Pereira et al. describe the chemical modification of SB by ethylenediaminetetraacetic (EDTA) dianhydride (EDTAD) in order to improve Zn2+ adsorption [14]. The EDTA molecule is a

O+

are predominant at pH lower than 6, while the groups on surface are proton-

), negatively affecting the interaction with the

widely used for the removal of heavy metals and dyes from wastewater [7–9].

**1.1. Sugarcane bagasse as a sorbent for heavy metals removal**

are associated with the hydronium ions (H3

route to attach carboxylic acid onto the cellulose.

**Figure 1.** Scheme of possible synthetic route for introduction of carboxylic groups.

and Cd(OH)+

adsorption is improved.

266 Sugarcane - Technology and Research

With the expansion of textile sector, dyes in wastewater have become a serious environmental problem. Dyes are organic chemical compounds that appear colored due to the presence of chromophore groups such as nitrous, azo, and carbonyl [19, 20]. The release of dye waste into water bodies affects the life in aquatic environments, causing the ruining of soils and poisoning


**Table 1.** SB in nature or modified as metal sorbent reported in the studies.

the auxochromes are important to enhance the affinity of the dye toward the fibers. As a result,

Sugarcane Bagasse As Potentially Low-Cost Biosorbent http://dx.doi.org/10.5772/intechopen.72153 269

Basically, dyes can be classified as cationic or anionic. **Figure 2** shows, for example, the molecules of erythrosin B (EB) and methylene blue (MB). Cationic dyes carry a positive charge in their molecule, while anionic dyes carry a negative charge [22–24]. In aqueous solution, the dye molecules will present positively or negatively charged as a function of pH, and the electrostatic interaction with the fiber surface will direct the adsorption process. Therefore, the dyes adsorption route by SB can be described in a similar way as observed for metal ions. At low pH, the surface of SB became positively charged and the cationic dye adsorption will decrease, while for anionic dyes the reverse process occurs. In contrast, at high pH, the cationic dye removal will increase because the surface appears negatively charged and the anionic dye adsorption became inhibited. **Table 2** summarizes some results of adsorption of

Research involving oil sorbents was firstly encouraged by the great environmental accidents generated by oil spills at sea [28–30]. In these cases, the adsorption processes are more suitable to remove and recover the oil. The sorbent material facilitates a transformation from liquid to solid phase, and then oil can be removed together with the sorbent. The main characteristic of crude oil sorbent material is the hydrophobicity and oleophilicity in order to attract oil preferentially to water. However, the amount of sorbents added to an oil polluted environment is a critical factor, because the inappropriate and excessive use can present subsequent waste disposal problems. It is especially important when organic synthetic products are used as sorbents. Synthetic sorbents, as polypropylene, do not degrade and are very expensive. Therefore, agricultural waste by-products were firstly used as an alternative oil sorbent to replace the conventional and nondegradable sorbent used to clean up oil spills. These biosorbents are biodegradable, renewable, abundant, and low cost. Teas et al. [31] compared the oil sorption capacity of cellulose with the expanded perlite and polypropylene in artificial seawater containing crude oil. These authors observed that for crude oil, the sorption capacity of cellulose overtakes the other sorbents. When light cycle oil and light gas oil were used in artificial seawater, they observed lower sorption by cellulose in relation to polypropylene, but similar behavior to expand perlite. The oil sorption capacity of vegetal fibers observed by several authors has been attributed to the interaction with hydrophobic sites in the biomass. Lignocellulosic fibers contain both hydrophilic and hydrophobic groups; however, the cellulose structure has hydrophilic nature with excellent wettability. The chemical functionalization of cellulose can increase its hydrophobic character, which is possible by changing the hydrophilic groups, hydroxyl (−OH) in the raw coir cellulose to hydrophobic hydrocarbons [32–34]. The biomass acetylation has been extensively used to increase its oil sorption capacity. Sun et al. [35] observed that SB acetylated presents greater machine

other studies that have been demonstrated the potential sorbent of agricultural by-products to

oil removal and the effect of biomass modification in the sorption capacity.

1) than polypropylene fibers (10 g g−1). **Table 3** summarizes

natural fiber, as SB, presents greater potential to remove dyes from wastewater.

**2. Sugarcane bagasse-based sorbents for motor oil removal**

dyes using SB, natural or modified, as a sorbent.

oil sorption capacity (13.5–20.2 g g<sup>−</sup>

**Figure 2.** Example of cationic (erythrosin B) and anionic (methylene blue) dyes.

of drinking water. Besides, dyes cannot be removed by conventional treatment methods, and are resistant to aerobic digestion. As an alternative method, physical removal of dyes from effluent through biosorption has been extensively studied [8, 21]. A dye molecule is characterized by the presence of chromophore groups, which are responsible for producing the color, and also by groups known as auxochromes such as carboxylic acid, sulfonic acid, amino, and hydroxyl groups. These auxochromes are responsible for impacting or shifting of a particular color when attached to a chromophore, and also used to influence the dye solubility. In fact,


**Table 2.** Examples of dyes adsorption by SB.

the auxochromes are important to enhance the affinity of the dye toward the fibers. As a result, natural fiber, as SB, presents greater potential to remove dyes from wastewater.

Basically, dyes can be classified as cationic or anionic. **Figure 2** shows, for example, the molecules of erythrosin B (EB) and methylene blue (MB). Cationic dyes carry a positive charge in their molecule, while anionic dyes carry a negative charge [22–24]. In aqueous solution, the dye molecules will present positively or negatively charged as a function of pH, and the electrostatic interaction with the fiber surface will direct the adsorption process. Therefore, the dyes adsorption route by SB can be described in a similar way as observed for metal ions. At low pH, the surface of SB became positively charged and the cationic dye adsorption will decrease, while for anionic dyes the reverse process occurs. In contrast, at high pH, the cationic dye removal will increase because the surface appears negatively charged and the anionic dye adsorption became inhibited. **Table 2** summarizes some results of adsorption of dyes using SB, natural or modified, as a sorbent.
